EP0482753A2 - Catalyseur pour le synthèse du méthanol - Google Patents

Catalyseur pour le synthèse du méthanol Download PDF

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EP0482753A2
EP0482753A2 EP91308468A EP91308468A EP0482753A2 EP 0482753 A2 EP0482753 A2 EP 0482753A2 EP 91308468 A EP91308468 A EP 91308468A EP 91308468 A EP91308468 A EP 91308468A EP 0482753 A2 EP0482753 A2 EP 0482753A2
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catalyst
methanol synthesis
precipitate
solution
elements
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EP0482753A3 (en
EP0482753B1 (fr
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Alkeos Sofianos
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Council for Scientific and Industrial Research CSIR
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/885—Molybdenum and copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/889—Manganese, technetium or rhenium
    • B01J23/8892—Manganese
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/15—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively
    • C07C29/151—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases
    • C07C29/153—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used
    • C07C29/154—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of oxides of carbon exclusively with hydrogen or hydrogen-containing gases characterised by the catalyst used containing copper, silver, gold, or compounds thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

  • THIS INVENTION relates to the synthesis of methanol. It relates in particular to a methanol synthesis catalyst precursor and to a method of forming such precursor; to a methanol synthesis catalyst and to a method of making such a catalyst; to an active methanol synthesis catalyst, and to a method of making thereof; and to a methanol synthesis process.
  • methanol from synthesis gas comprising mixtures of hydrogen and carbon oxides in predetermined ratios, and derived from coal or natural gas.
  • These processes use copper-zinc-aluminium or copper-zinc-chromium mixed oxide catalysts.
  • These catalysts exhibit relatively high activity and selectivity in low pressure synthesis of methanol using fixed-bed type reactors; however, their thermal stability and durability over long periods of time, their abrasion resistance, and their tolerance to catalyst poisons are generally low, so that they cannot be used in slurry type or fluidized bed reactors.
  • a method of forming a methanol synthesis catalyst precursor which method comprises forming a precipitate comprising compounds, thermally decomposable to oxides or mixed oxides, of copper, zinc, aluminium and at least one element of Group IVB and/or Group VIIB of the Periodic Table of Elements.
  • Periodic Table of Elements referred to is that in general usage, for example, that depicted on page 21 of Volume 10 of McGraw-Hill Encyclopedia of Science and Technology, 5th Edition, published in 1982 by McGraw-Hill Book Company.
  • the copper, zinc, aluminium and the element or transition metal of Group IVB and/or Group VIIB may initially be in the form of soluble compounds, preferably compounds which are soluble in an acid medium.
  • soluble compounds preferably compounds which are soluble in an acid medium.
  • examples of such compounds are nitrate, formiate, carbonate, acetate, citrate and oxalate salts of the metals.
  • the elements are initially in their soluble nitrate form.
  • the element of Group IVB when present, may be titanium, zirconium or hafnium, but zirconium is preferred. From Group VIIB, when present, manganese is preferred because of its ready availability. While the manganese can be used in solution in its nitrate form as hereinbefore described, it can instead be added as permanganate or as manganous acetate during granulation and prior to pelleting of the catalyst, as hereinafter described.
  • the precipitate may also include a compound, thermally decomposable to anoxide, of at least one element of Group VIB of the Periodic Table of Elements. This element may also initially be in the form of a soluble compound.
  • the element of Group VIB may initially be in the form of a thermally decomposable ammonium salt.
  • the element of Group VIB can thus be chromium, molybdenum or tungsten. Molybdenum is preferred in view of its promotor and poison removal capabilities, but chromium or tungsten will also give some benefit.
  • the molybdenum may then be used in ammonium paramolybdate form which is readily soluble in ammonia-containing distilled water to form the thermally decomposable ammonium salt thereof.
  • the precipitate may be formed by admixing solutions of the elements; heating the resultant mixture to its precipitation temperature; heating a solution of a precipitant in water; and thereafter adding both solutions to preheated demineralized water with vigorous stirring and strict pH control, eg in a precipitation reactor.
  • the precipitate may be formed by admixing solutions of the elements; heating the resultant mixture to its precipitation temperature; and adding the preheated mixture or solution of elements rapidly to a predetermined or controlled volume of a preheated solution of a precipitant in water.
  • the precipitate may be formed by admixing solutions of the elements; heating the resultant mixture to its precipitation temperature; and adding a solution of precipitant in water, preheated to a predetermined precipitation temperature, to the hot solution or mixture of the elements, while stirring vigorously, until a predetermined pH value of the hot solution or mixture to which the precipitant solution is added, is reached.
  • the precipitate may then be separated from the residual liquid after allowing the liquid to stand under stirring and at the precipitation temperature for a period of time, eg for between 0.5 and 60 minutes, for maturation of the catalyst precursor.
  • the reactor vessel will thus naturally be allowed to stand under stirring as hereinbefore described.
  • the separation may be effected by filtration.
  • the precipitate may be resuspended at least once, but typically a few times, in demineralized water, separated from the water by filtration, and finally washed thoroughly on the filter to remove as much alkali metal as possible
  • the precipitant may be a solution of sodium, potassium and/or ammonium carbonate or bicarbonate in water.
  • the precipitation may be carried out at high temperature, eg between about 75°C and 100°C. Lower temperatures, eg between about 50°C and 60°C may also be used, but the crystallite size of the catalyst precursor so formed is larger, and the activity of a catalyst formed therefrom, lower.
  • the precipitation may be effected at a pH in the range of 6.5-9.5.
  • the washed precipitate comprising a homogeneous hydrated precursor may then be dried by any known drying process, for example in an oven at temperatures between 50°C and 130°C, under vacuum or at normal pressure. Alternatively spray drying may be employed.
  • the dried precipitate or precursor thus obtained comprises an essentially homogeneous association of carbonates and hydroxycarbonates with a potential oxide content of between 65% and 80%.
  • a method of forming a methanol synthesis catalyst precursor which method comprises forming a precipitate comprising compounds, thermally decomposable to oxides or mixed oxides, of copper, zinc, aluminium as well as at least one element of Group VIB of the Periodic Table of Elements.
  • the copper, zinc and aluminium may initially be in soluble nitrate form, while the element of Group VIB may initially be in the form of a thermally decomposable ammonium salt.
  • the element of Group VIB may be molybdenum, which is initially in the form of ammonium paramolybdate which is readily soluble in ammonia-containing distilled water to form the thermally decomposable ammonium salt thereof.
  • the precipitate may be formed as hereinbefore described with respect to the first aspect of the invention.
  • the invention extends also to a methanol synthesis catalyst precursor, when formed by one of the methods hereinbefore described.
  • a method of making a methanol synthesis catalyst which comprises calcining a dried precursor as hereinbefore described.
  • the calcination may comprise treating the dried precipitate at a temperature of between 200°C and 450°C, preferably between 250°C and 350°C, for between 3 and 10 hours, to obtain a homogeneous catalyst.
  • the catalyst comprising a homogeneous mixture of copper, zinc, aluminium, and elements of Groups IVB, VIB and VIIB as hereinbefore described still contains between 10% and 15% volatiles.
  • the homogeneous catalyst may be densified and pelletized after addition thereto of 1-3%, preferably about 2%, graphite to facilitate densification and pelleting.
  • the invention extends further to a methanol synthesis catalyst, when formed by the method as hereinbefore described.
  • a methanol synthesis catalyst which comprises as a first component, an admixture of copper oxide and zinc oxide; and as a second component, an admixture of aluminium oxide and an oxide of an element of Group IVB of the Periodic Table of Elements and/or an oxide of an element of Group VIIB of the Periodic Table of Elements, with the first component being in intimate admixture with the second component.
  • the Group IVB element when present, may be zirconium, while the Group VIIB element, when present, may be manganese.
  • the first component may also include an oxide of at least one element of Group VIB of the Periodic Table of Elements.
  • the element of Group VIB, when present, may be molybdenum.
  • the catalyst may comprise, in terms of metal atoms, 30-70% copper, 20-50% zinc, 2-20% aluminium, 1-15% zirconium, 0.5-5% manganese and 0.1-1% molybdenum.
  • an active methanol synthesis catalyst which comprises subjecting a catalyst as hereinbefore described to thermal activation treatment, to produce an active catalyst in which at least a portion of one or more of the copper, zinc, and, when present, element of Group VIB, is in metallic form.
  • the thermal activation may comprise reduction treatment of the calcined catalyst in situ after it has been charged into a methanol synthesis reactor, using a mixture of an inert gas, preferably nitrogen, and at least one reducing gas, such as hydrogen, carbon monoxide or a mixture thereof.
  • the molar ratio between reducing gas and inert gas should be between 1:30 and 1:100.
  • the reduction temperature may be between 100°C to 280°C, preferably between 130°C and 240°C, and the pressure may be 0.1 to 1 MPa.
  • the catalyst is preferably first slowly heated up under the inert gas and under a pressure of between 0.6-0.9 MPa, until a temperature of between 120°C and 150°C has been reached, using a temperature program, at a rate of between 30-50°C/hour. Theieafter the reduction is allowed to take place by adding the reducing gas to the inert gas in a molar ratio as described above, but preferably between 1:50 and 1:40. The temperature is then slowly further increased using a second temperature program, at a rate of 15-25°C/h to reach 190-210°C. The thermal reductive activation is then continued at the temperature of 190-210°C for a time period of between 10 and 24 hours.
  • the temperature can be increased to between 230°C and 250°C and the molar ratio of reducing gas to inert gas to between 1:10 and 1:6 for a time period of 1-3 hours, in order to complete activation.
  • the invention extends also to an active methanol synthesis catalyst, when produced by the method as hereinbefore described.
  • a process of methanol synthesis which comprises reacting carbon monoxide and/or carbon dioxide with hydrogen in the presence of an active methanol synthesis catalyst as hereinbefore described.
  • the methanol synthesis reaction may be conducted at a reaction temperature of between 180°C and 300°C, and at a reactor pressure of between 3 and 12 MPa, preferably 4-10 mPa.
  • the synthesis gas may comprise (on a molar basis) 60-80% hydrogen, 5-30% carbon monoxide, 3-10% carbon dioxide, 0-5% methane and 0-10% inert gases, such as nitrogen, helium, argon and the like.
  • the gas hourly space velocity ie the volume of the gas mixture (NTP) passed per volume of the catalyst bed per hour, may be from 2000 to 50000 v/vh, preferably from 4000 to 20000 v/vh.
  • methanol production by means of catalysis, from synthesis gas, is known, and methanol is assuming increasing importance for the manufacture of synfuels, chemical feedstocks such as formaldehyde and specialty chemicals, as well as for its use for the production of fuel additives.
  • methanol synthesis catalysts should not have the drawbacks set out hereinbefore, ie the catalysts should have high catalytic activity, good heat resistance and durability, and good abrasion resistance.
  • the catalysts of the present invention comply with these requirements.
  • catalysts for the low pressure methanol synthesis should also be tolerant to poisons such as sulphur and chlorine compounds or they should contain components which should preferably absorb these poisons, thus protecting the catalytically active components of the system for the methanol synthesis.
  • poisons such as sulphur and chlorine compounds
  • Many methanol synthesis catalysts containing copper and zinc are highly sensitive to such poisons, and their catalytic performance may be severely restricted when the feed syngas contains rests of sulphur or chlorine.
  • the catalysts of the present invention are, however, less sensitive to these poisons.
  • methanol synthesis When activated and ready for use methanol synthesis should be of an essentially homogeneous composition, and should have an alkali concentration as low as possible. Iron contamination should also be avoided as far as possible not only because under the synthesis conditions this element may form iron carbonyls with the synthesis gas but also for its activity towards the formation of Fischer-Tropsch products and the decrease in selectivity of the methanol synthesis reaction.
  • methanol synthesis catalysts should primarily consist of copper oxide crystallites not greater than 10 nanometers (100 Angstrom units) and preferably in the range 3.0-5.5 mm (30-55 ⁇ ).
  • the specific surface area of the mentioned catalysts should vary between 50 and 160 m2 g ⁇ 1. Again, the catalysts of the present invention comply with these requirements to a large degree.
  • the catalytic performance of known basic copper-zinc-aluminium catalyst is considered to be dependent on the formation of a bi-phasic precursor, ie a catalytically active phase containing copper stabilized by zinc oxide via an epitaxial growth mechanism and through free zinc oxide, and a zinc aluminate phase which gives good mechanical strength to the catalyst because of its refractory properties.
  • the aluminium content of the catalyst while being of importance for its overall catalytic performance (especially as regards the mechanical properties of the catalytic systems), should be kept within limits (in most cases less than 10%, expressed as alumina). Higher alumina concentrations in the catalyst lead to the formation of acidic centres on the catalyst surface and to a dehydration of the product methanol to dimethylether with a simultaneous drop in the selectivity of the methanol synthesis. However, a decrease in the alumina content to less than 5% is detrimental to the overall stability of the catalyst and requires the addition of further structural promoters such as the amphoteric oxides of manganese, zirconium, and others.
  • Catalyst A (a basic low-pressure methanol synthesis catalyst) was prepared as follows:
  • Copper nitrate, Cu(NO3)2.3H2O (241.593 g) was dissolved in 2 l demineralized water to form a 0.5 M solution (solution X).
  • zinc nitrate, Zn(NO3)2.6H2O (297.468 g) was dissolved in demineralized water (2 l ) to form a 0.5 M solution (solution Y).
  • Aluminium nitrate, Al(NO3)3.9H2O 1500.516 g was dissolved in 2 l demineralized water in a volumetric flask to form a 2 M solution (solution Z).
  • An aqueous 10% solution of sodium hydrogen carbonate, NaHCO3, was produced by dissolving 500 g of the salt in 5 l demineralized water.
  • a solution comprising 371.7 ml of solution X, 180.7 ml of solution Y and 28.25 ml of solution Z was prepared and heated up to approximately 80°C. This solution was added concurrently with sufficient of the abovementioned 10% sodium bicarbonate solution (maintained at 80°C) into a reactor vessel containing 500 ml preheated demineralized water (80°C), under vigorous stirring, to ensure a slurry pH of 7.0 ⁇ 0.02 at all times. Precipitation commenced immediately and after precipitation was completed, the slurry was allowed to digest in the mother liquor at 80°C and a pH of 7.0 for 1 hour.
  • the precipitate was filtered off, washed thoroughly with 10 l hot (80-90°C) demineralized water to remove all traces of sodium ions, dried overnight at 110°C and calcined at 350°C for 5 hours, to produce a catalyst precursor.
  • compression moulding pressure: 2.5 tonnes
  • Catalyst B was prepared according to a procedure similar to that described in GB Patent 2047556:
  • the aqueous solution containing the copper nitrate and the sodium aluminate was rapidly added to the ammonium bicarbonate solution, with constant stirring, and a precipitation reaction took place.
  • a copper-aluminium slurry was thus formed and maintained at this temperature (30°C).
  • the zinc oxide slurry was added under vigorous stirring to the copper-aluminium slurry and thereafter a stream of gaseous carbon dioxide (CO2) was bubbled into the slurry at a rate of 50 mol/min for 2 hours.
  • CO2 gaseous carbon dioxide
  • the temperature of the slurry was rapidly increased to 80°C and maintained at this level for another 30 minutes.
  • the resulting Cu-Zn-Al catalyst precursor was filtered, washed thoroughly with an excess of hot (80°C) demineralized water, dried overnight and finally calcined following the same procedure as for catalyst A in Example 1 (350°C, 5 hours). After calcination, the resulting Cu-Zn-Al catalyst had a Cu:Zn:Al atom ratio of 54,5:42.15:3.35.
  • Catalyst AZr1.5 was prepared in an analogous procedure to the one described in Example 1: For approximately 25.375 g of the catalyst, 14.75 g CuO, 7.35 g ZnO, 2.88 g Al2O3, and 0.375 g ZrO2 from the corresponding nitrate salt solutions were used. Thus, 372 ml of solution X were mixed with 181 ml of solution Y and 29 ml of solution Z. In this example, 26 ml of a 40 g/ l Zr(NO3)4.5H2O were added to the above.
  • the above quantities of the nitrate solutions were thoroughly mixed, preheated at 80°C and then added via a dropping funnel, under vigorous stirring, to 500 ml preheated (80°C) demineralized water simultaneously with sufficient NaHCO3 solution to maintain a pH of 7.
  • the catalyst precursor preparation was completed as in Example 1.
  • the calcined catalyst AZr1.5 was otherwise identical to catalyst A, except that it contained 1.5% ZrO2 in addition to the quantities, of CuO, ZnO, and Al2O3 specified in Example 1.
  • the Cu:Zn:Al:Zr atom ratio was found to be 60.5:30.3:7.8:1.4, and its specific surface area was 66 m2/g.
  • Example 3 was repeated except that the catalyst composition was changed in that, for the preparation of approximately 25.75 g catalyst, the amount of zirconium nitrate solution added was increased to 52 ml (hence corresponding to a total quantity of 0.75 g ZrO2).
  • the catalyst obtained was designated AZr3 and it contained 3% ZrO2 in addition to the quantities of CuO, ZnO, and Al2O3 specified in Example 1.
  • the Cu:Zn:Al:Zr atom ratio was found to be 59.6:29.9:7.7:2.8, and its specific surface area was 69 m2/g.
  • Example 4 was repeated, save that the catalyst composition was further varied in that, for the preparation of approximately 26,25 g catalyst 86 ml of the abovementioned zirconium nitrate solution (corresponding to 1.25 g ZrO2) was added and hence the catalyst obtained, designated AZr5, contained 5% ZrO2 in addition to the quantities of CuO, ZnO, and Al2O3 specified in Example 1.
  • the resulting catalyst after calcination, had a Cu:Zn:Al:Zr atom ratio of 58.5:29.3:7.6:4.6, with a specific surface area of 78 m2/g.
  • the preparation of catalyst AZr3Mo was the same as in Example 4 except that 0.207 g MoO3 as ammonium paramolybdate was added to the nitrates solution in order to prepare a catalyst promoted with 0.5% Mo, as MoO3, in addition to the quantities of CuO, ZnO, Al2O3 and ZrO2 specified in Example 4.
  • the Cu:Zn:Al:Zr:Mo metal atom ratio of the resultant catalyst was 59.2:29.7:7.7:2.8:0.6.
  • the specific surface area of the catalyst was found to be 99 m2/g.
  • the crystal size of copper therein was found to be 45 ⁇ (using x-ray diffractrometry).
  • the preparation of catalyst AZr5Mo1 was the same as in Example 5 except that 0. 207 g MoO3 as an ammonium paramolybdate solution was added to the nitrates solution in order to prepare a catalyst promoted with 0. 5% Mo as MoO3 in addition to the quantities of CuO, ZnO, Al2O3 and ZrO2 specified in Example 5.
  • the Cu:Zn:Al:Zr:Mo metal atom ratio of the resultant catalyst was 58.2:29.1:7.5:4.6:0.6.
  • a specific surface area of 126 m2/g was determined by BET.
  • a copper crystallite size of 40 ⁇ was measured by x-ray diffractrometry.
  • Example 6 The procedure of preparation of Example 6 was repeated except that 0.25 g Mn as manganese nitrate solution was added to the other nitrates solution.
  • the catalyst obtained was designated AZr3Mn1Mo1, and its Cu:Zn:Al:Mn:Zr:Mo metal atom raio was 58.5:29.3:7.5:1.2:2.8:0.7.
  • the surface area was found to be 130 m2/g, and its copper crystallite size 40 ⁇ .
  • Example 7 The procedure of preparation of Example 7 was repeated except that 0.25 g Mn as manganese nitrate solution was added to the other nitrates solution.
  • the catalyst obtained was designated AZr5Mn1Mo1, and its Cu:Zn:Al:Mn:Zr:Mo metal atom ratio was 57.4:28.7:7.4:1.2:4.6:0.7.
  • a specific surface area of 136 m2/g was determined by BET, and a copper crystallite size of 40 ⁇ was found using x-ray diffractrometry.
  • the catalyst precursor of this example has the same composition as that obtained in Example 9; however the preparation procedure was different: 371.7 ml of solution X (see Example 1), 180.7 ml of solution Y, 28.25 ml of solution Z, 86 ml of the zirconium nitrate solution of Example 5 corresponding to 1. 25 gm ZrO2 and 5. 75 ml of a manganese nitrate solution containing 0.25 g Mn were thoroughly mixed and then heated to 80°C in an electric water bath, to produce Mixture A.
  • the nitrates mixture (Mixture A) was added under vigorous stirring to the precipitation reactor. The time of precipitation was 1 minute. The precipitate was subsequently allowed to digest for 1 hour at 80°C in the mother liquor. The pH fell initially to 6.5 but rose at the end of the 1 hour digestion period to reach a value of 7.00.
  • the contents of the precipitation reactor were then filtered through a sintered glass filter funnel, and the filter cake washed thoroughly with 10 litres boiling demineralized water. After filtration the catalyst precursor was dried overnight at 110°C and then calcined at 300°C for 7 hours.
  • the catalyst obtained was designated A2Zr5Mn1Mo1, and had the same composition as in Example 9; however its method of preparation was different.
  • the surface area of the above catalyst was found to be 140 m2/g using BET, and its copper crystallite size was 40 ⁇ using x-ray diffractrometry.
  • Catalyst A3Zr5Mn1 was prepared in an analogous procedure to that described in the previous examples.
  • To make approximately 25 g of the catalyst 5.625 g CuO, 13.125 g ZnO, 4.25 g Al2O3, 1.50 g ZrO2 and 0.50 g MnO2 from the corresponding nitrate salt solutions were mixed thoroughly together to make up 625 ml of solution X.
  • the contents of the precipitation reactor were then filtered according to the procedure described in the previous examples.
  • the filter cake was first washed while on the filter using 2 liters boiling deionized water. Then, the filter cake was suspended in 2 liters boiling deionized water and refiltered. This procedure was repeated 3 times more, using a total of 10 liters deionized water.
  • the catalyst precursor thus formed was dried for 16 hours at 110°C and calcined at 280°C for 6 hours.
  • the calcined catalyst formed was suspended in 100 ml of a 1% solution of NH4OH for 1 hour under slow stirring, dried at 110°C for 1 hour, and calcined at 280°C for an additional hour.
  • the final catalyst was found to have a BET surface area of 160 m2/g, a specific copper surface area of 29 m2/g, as measured by N2O chemisorption, and a Cu crystallite size of 30 ⁇ .
  • the residual K content was less than 1 ppm.
  • the experimental apparatus 10 comprises pressurized cylinders 12, 14, 16 and 18 containing CO, H2, CO2 and N2 respectively.
  • a flow line 20 fitted with a pressure regulator 22, a purifier and filter 24, solenoid valves 26, a vent line 28 fitted with a needle control valve 30, a mass flow controller 32, a further vent line 28, a three-way solenoid valve 34, a 20 micron filter 36, a quick connector 38, to a reactor 40 fitted with a thermocouple 42.
  • a flow line 50 fitted with a regulator 22, purifier and filter 24, valves 26, vent line 28, and flow controller 32.
  • the line 50 leads into the line 20 downstream of a pressure transducer 52.
  • the line 50 is also fitted with a pressure relief valve 54.
  • a heated flow line 60 leads from the reactor 40 and is fitted with a quick connector 38, a filter 36, a three-way valve 34 (connected by means of a flow line 62 to the other three-way valve 34), a pressure gauge 64, a back-pressure regulator 66, a gas sampling valve 68, a condenser 70, a further three-way valve 34, a bubbler 72 and a soap-film flow meter 74.
  • a flow line, fitted with a wet gas meter 76 leads from the last three-way valve 34, to vent.
  • the reactant gases (CO, CO2 and hydrogen) as well as the nitrogen used for catalyst activation, were fed into the microreactor 40 after being purified. Brooks mass flow measuring and control systems 32 were used for individually controlling the flow rate of each gas and for establishing the gas mixtures required.
  • the product stream from the reactor passed through the heated line 60 and after the pressure was reduced by a Tescom back-pressure regulator 66 the stream was sampled by an On-Line Carlo Erba gas chromatograph (not shown) equipped with a multi-port injection valve, through the valve 68. In all cases a reactant gas composition of 63.2% H2, 31.9% CO and 4.9% CO2 was used for methanol synthesis tests.
  • the procedure adopted for catalyst activation was similar to the one used in commercial methanol plants.
  • the catalyst was slowly heated up to 130°C (50°C/h) under a flow of nitrogen (4 L/Kg cat /h). At this temperature, hydrogen was added to the nitrogen stream to a level of 2.5% and the temperature was further raised to 200°C (20°C/h). The activation was continued for 16 h at this temperature. Thereafter the hydrogen concentration of the inert gas was further increased to 12% and the temperature was raised to 240°C. After 2 hours at this temperature the catalyst was ready for operation and the temperature was adjusted to 200°C for the first test.
  • the various methanol synthesis catalysts prepared as described in the examples were suitably sized (300-500 ⁇ m) for charging to the microreactor.
  • the catalyst powders obtained after calcination were pressed into tablets, crushed and sieved to size.
  • STY space-time-yield
  • the synthesis gas containing 31.9% CO, 4.9% CO2 and 63.2% H2 was contacted with the catalyst at a temperature in the range from 180-325°C.
  • operation of the process at temperatures above 300°C tended to increase production of various by-products such as dimethylether, higher alcohols and gaseous hydrocarbons, at the expense of the selectivity to methanol.
  • an operating temperature between 180°C and 275°C should be chosen. Nevertheless, tests above this temperature range (up to 325°C) were carried out to demonstrate the improved thermal stability of the catalysts of the present invention in comparison with known catalysts.
  • the operating pressure is preferably in the range of 2.0-10.0 MPa and the gas hourly space velocity was varied over a wide range from 4000 to 20000 hour ⁇ 1.
  • a pressure of 4.0 MPa was used while the GHSV was maintained at a value of 8000 v/vh, except as otherwise specified.
  • the catalysts in accordance with the invention generally exhibit improved catalytical activity at very low and very high reaction temperatures for the methanol synthesis, as compared to the reference catalysts, as is evident from Table 2.
  • a further advantage of the catalysts of the invention is that they demonstrate enhanced mechanical stability and attrition resistance as compared to the reference catalysts, which renders them suitable for other methanol synthesis processes, eg fluidized bed and slurry reactor operation.
  • the presence of the molybdenum enhances catalyst resistance to poisons such as sulphur and chlorine.

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EP91308468A 1990-09-18 1991-09-17 Catalyseur pour le synthèse du méthanol Expired - Lifetime EP0482753B1 (fr)

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EP0573087A2 (fr) * 1992-05-07 1993-12-08 Dsm N.V. Hydrogénation d'acide benzoique et catalysateur convenant à cette préparation
WO1994021376A1 (fr) * 1993-03-19 1994-09-29 Patlico International B.V. Synthese d'alcools superieurs
EP0721799A1 (fr) * 1995-01-11 1996-07-17 United Catalysts, Inc. Catalyseur en oxyde de cuivre et oxyde de zinc stabilisé et activé et procédé pour sa préparation
EP0742193A1 (fr) * 1995-05-11 1996-11-13 Mitsubishi Gas Chemical Company, Inc. Procédé pour la fabrication du méthanol et procédé pour la fabrication de catalyseur pour la synthèse du méthanol
EP0864360A1 (fr) * 1997-03-11 1998-09-16 Agency of Industrial Science and Technology Catalyseur de synthèse du méthanol à base d'oxyde de cuivre et de zinc et procédé de preparation de ce dernier
US6147125A (en) * 1996-05-13 2000-11-14 Nkk Corporation Method and apparatus for producing dimethyl ether
WO2004060556A1 (fr) * 2002-12-17 2004-07-22 Sud-Chemie Inc. Catalyseur de conversion a la vapeur d'eau
EP1440731A2 (fr) * 2002-11-08 2004-07-28 Süd-Chemie Ag Ce/Cu/Mn-Catalyseurs et procédé pour leur fabrication
US6800665B1 (en) 1996-05-13 2004-10-05 Jfe Holdings, Inc. Method for producing dimethyl ether
WO2006117190A1 (fr) * 2005-05-03 2006-11-09 Süd-Chemie AG Production de catalyseurs cu/zn/al par voie de formates
WO2013072197A1 (fr) * 2011-11-16 2013-05-23 Süd-Chemie Ip Gmbh & Co. Kg Catalyseur de synthèse de méthanol sur la base de cuivre, zinc et aluminium
KR101372237B1 (ko) * 2012-02-28 2014-03-11 한국에너지기술연구원 이산화탄소로부터 메탄올 제조용 복합금속산화물 촉매의 제조 방법, 이 촉매를 이용한 메탄올 제조 방법
CN110252302A (zh) * 2019-06-25 2019-09-20 陕西延长石油（集团）有限责任公司 一种催化甲烷低温选择性氧化制备甲醇的催化剂及其制备方法与应用
WO2019238634A1 (fr) 2018-06-12 2019-12-19 Haldor Topsøe A/S Processus de production de méthanol utilisant un catalyseur à faible teneur en fer
CN112657500A (zh) * 2021-01-07 2021-04-16 常州大学 一种高稳定性铜基甲醇合成催化剂的制备方法

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KR100812099B1 (ko) * 2006-11-28 2008-03-12 한국가스공사 디메틸에테르 제조용 혼합촉매, 이의 제조방법 및 이를 이용한 디메틸에테르 제조방법
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WO2010078035A2 (fr) 2008-12-17 2010-07-08 Synch Energy Corporation Procédé et système pour transformer du biogaz en combustibles liquides
BR112012011076A2 (pt) * 2009-11-10 2016-07-05 Shell Int Research processo e sistema integrado para a preparação de um produto de olefina inferior.
WO2011057976A2 (fr) 2009-11-10 2011-05-19 Shell Internationale Research Maatschappij B.V. Procédé de production d'oléfines
WO2011057978A2 (fr) * 2009-11-10 2011-05-19 Shell Internationale Research Maatschappij B.V. Procédé pour la préparation d'un produit oléfinique inférieur
RU2547146C2 (ru) * 2009-11-10 2015-04-10 Шелл Интернэшнл Рисерч Маатсхаппий Б.В. Способ получения этиленоксида
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BR112012027099A2 (pt) 2010-04-23 2016-07-26 Shell Int Research processo para a produção de hidrocarbonetos aromáticos e de etileno, uso de hidrogênio, e, sistema integrado para a produção de olefinas
GB2554618B (en) 2015-06-12 2021-11-10 Velocys Inc Synthesis gas conversion process
CN115532291B (zh) * 2021-06-29 2023-11-28 中国石油化工股份有限公司 一种甲醇合成催化剂的保护剂及其制备方法和应用

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Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0528305A2 (fr) * 1991-08-17 1993-02-24 Hoechst Aktiengesellschaft Catalyseurs contenant cuivre, oxyde de zinc et alumine
EP0528305A3 (en) * 1991-08-17 1993-03-17 Hoechst Aktiengesellschaft Catalysts containing copper-zincoxide-aluminiumoxide
US5302569A (en) * 1991-08-17 1994-04-12 Hoechst Aktiengesellschaft Copper/zinc oxide/aluminum oxide-containing catalysts
EP0573087A2 (fr) * 1992-05-07 1993-12-08 Dsm N.V. Hydrogénation d'acide benzoique et catalysateur convenant à cette préparation
EP0573087A3 (fr) * 1992-05-07 1994-04-13 Dsm Nv
WO1994021376A1 (fr) * 1993-03-19 1994-09-29 Patlico International B.V. Synthese d'alcools superieurs
US5627295A (en) * 1993-03-19 1997-05-06 Patlico International Bv Synthesis of higher alcohols
EP0721799A1 (fr) * 1995-01-11 1996-07-17 United Catalysts, Inc. Catalyseur en oxyde de cuivre et oxyde de zinc stabilisé et activé et procédé pour sa préparation
EP0742193A1 (fr) * 1995-05-11 1996-11-13 Mitsubishi Gas Chemical Company, Inc. Procédé pour la fabrication du méthanol et procédé pour la fabrication de catalyseur pour la synthèse du méthanol
US5767039A (en) * 1995-05-11 1998-06-16 Mitsubishi Gas Chemical Company, Inc. Process for manufacturing methanol and process for manufacturing catalyst for methanol synthesis
US6562306B1 (en) 1996-05-13 2003-05-13 Nkk Corporation Apparatus for producing dimethyl ether
US6800665B1 (en) 1996-05-13 2004-10-05 Jfe Holdings, Inc. Method for producing dimethyl ether
US7033972B2 (en) 1996-05-13 2006-04-25 Jfe Holdings, Inc. Catalyst for producing dimethyl ether, method for producing catalyst and method for producing dimethyl ether
US6147125A (en) * 1996-05-13 2000-11-14 Nkk Corporation Method and apparatus for producing dimethyl ether
EP0864360A1 (fr) * 1997-03-11 1998-09-16 Agency of Industrial Science and Technology Catalyseur de synthèse du méthanol à base d'oxyde de cuivre et de zinc et procédé de preparation de ce dernier
EP1440731A2 (fr) * 2002-11-08 2004-07-28 Süd-Chemie Ag Ce/Cu/Mn-Catalyseurs et procédé pour leur fabrication
EP1440731A3 (fr) * 2002-11-08 2005-02-02 Süd-Chemie Ag Ce/Cu/Mn-Catalyseurs et procédé pour leur fabrication
WO2004060556A1 (fr) * 2002-12-17 2004-07-22 Sud-Chemie Inc. Catalyseur de conversion a la vapeur d'eau
WO2006117190A1 (fr) * 2005-05-03 2006-11-09 Süd-Chemie AG Production de catalyseurs cu/zn/al par voie de formates
US7820128B2 (en) 2005-05-03 2010-10-26 Sud-Chemie Ag Production of Cu/Zn/A1 catalysts via the formate route
WO2013072197A1 (fr) * 2011-11-16 2013-05-23 Süd-Chemie Ip Gmbh & Co. Kg Catalyseur de synthèse de méthanol sur la base de cuivre, zinc et aluminium
KR101372237B1 (ko) * 2012-02-28 2014-03-11 한국에너지기술연구원 이산화탄소로부터 메탄올 제조용 복합금속산화물 촉매의 제조 방법, 이 촉매를 이용한 메탄올 제조 방법
WO2019238634A1 (fr) 2018-06-12 2019-12-19 Haldor Topsøe A/S Processus de production de méthanol utilisant un catalyseur à faible teneur en fer
CN110252302A (zh) * 2019-06-25 2019-09-20 陕西延长石油（集团）有限责任公司 一种催化甲烷低温选择性氧化制备甲醇的催化剂及其制备方法与应用
CN112657500A (zh) * 2021-01-07 2021-04-16 常州大学 一种高稳定性铜基甲醇合成催化剂的制备方法
CN112657500B (zh) * 2021-01-07 2023-04-11 常州大学 一种高稳定性铜基甲醇合成催化剂的制备方法

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ATE145837T1 (de) 1996-12-15
EP0482753A3 (en) 1992-08-05
EP0482753B1 (fr) 1996-12-04
US5254520A (en) 1993-10-19

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